CN108017091A - A kind of rod-like nano α-MnO2And its preparation method and application - Google Patents

A kind of rod-like nano α-MnO2And its preparation method and application Download PDF

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CN108017091A
CN108017091A CN201711083081.6A CN201711083081A CN108017091A CN 108017091 A CN108017091 A CN 108017091A CN 201711083081 A CN201711083081 A CN 201711083081A CN 108017091 A CN108017091 A CN 108017091A
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mno
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冯林
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Shenzhen City Tezhi Made Crystal Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides; Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13—Nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area

Abstract

The invention discloses a kind of nanometer α MnO2Preparation method and catalytic applications, concretely comprise the following steps：1) dissolving analyzes pure level potassium permanganate and obtains solution A under the conditions of magnetic agitation；2) dilute nitric acid solution control PH is then added dropwise and obtains B solution；3) dissolving analyzes pure level manganese sulfate and obtains solution C under the conditions of magnetic agitation；4) solution B is added drop-wise in solution C dropwise under the conditions of magnetic agitation and obtains mixing turbid solution D；5) circulating water type vacuum pump is filtered and washed for several times repeatedly；6) gained sample microwave combustion method 600s after filtering；7) final acquisition nanometer α MnO are ground after oven drying2Catalyst.Nanometer α MnO of the present invention2Synthesis step it is simple, synthesis cycle is short, without high-temperature roasting, requires no long-time heat preservation processing and the numerous and diverse preparation process of collosol and gel of hydro-thermal treatment method；In addition, the nanometer α MnO of this method synthesis2With preferable purity and the uniformity.It is final to obtain catalyst, in NH3There can be good Reduction of NO under existence conditionXPerformance.

Description

A kind of rod-like nano α-MnO2And its preparation method and application
Technical field
The invention belongs to materials science field, and in particular to a kind of rod-like nano α-MnO2 and preparation method thereof and should With.
Background technology
Manganese dioxide crystal aboundresources, it is cheap, based on [MnO6] is octahedra, form a variety of crystalline structures. The manganese dioxide of different crystal forms has a wide range of applications in fields such as catalysis, ultracapacitor, ceramics and electronics.By grinding for many years Study carefully discovery, manganese dioxide mainly there are five kinds of crystalline structures, is α, β, γ, δ and λ respectively, and the titanium dioxide of different crystal forms structure The physical and chemical properties of manganese have larger difference.Nanometer α-MnO2With larger specific surface area and surface energy, therefore wherein It is the most extensive in the application and research of catalytic field.Nowadays nanometer α-MnO2Synthetically prepared mainly have two kinds of sides Method, is hydro-thermal method and sol-gal process respectively.Hydro-thermal method is by the way that mixed reactant is transferred in reaction kettle, is passed through for a long time Temperature is controlled to form the manganese dioxide of required crystal form.But hydro-thermal method synthesis nanometer α-MnO2Long preparation period, and be limited In reaction kettle container capacity, it is less that sample quality is prepared every time.In addition, sol-gal process preparation process is relatively complicated, and make The standby time is also longer.This two kinds of synthetic methods have certain limitation, therefore study a kind of facile syntheesis nanometer α-MnO2's Method has actual application value.
Nanometer α-MnO22 × 2 pore passage structures are combined into based on [MnO6] octahedron, these pore passage structures improve Nanometer α-MnO2Specific surface area, make it have more avtive spot, thus show preferable catalytic performance so that nanometer α-MnO2There is very wide application prospect in catalytic field.
The content of the invention
The defects of in order to overcome the prior art, the purpose of the invention is to provide a kind of rod-like nano α-MnO2And its system Preparation Method, catalyst preparation process flow of the present invention is simple and convenient to operate, cost is low, without reaction kettle hydro-thermal process, without By numerous and diverse step of collosol and gel, prepared nanometer α-MnO2Into bar-shaped, surface nature is very excellent, has excellent urge Change activity.
It is a further object to provide the nanometer α-MnO prepared by the preparation method2As low temperature selective catalysis Reduce NOXApplication.
To achieve the object of the present invention, the technical solution used in the present invention is：
A kind of rod-like nano α-MnO2Preparation method, comprise the following steps：
(1) a certain amount of analytically pure potassium permanganate is dissolved in deionized water, it is complete in being stirred well under room temperature Dissolving, obtains solution A；
(2) 0.1mol/L dilute nitric acid solutions are added dropwise into solution A, adjusts PH to 6 or so, continues to stir evenly, obtain solution B；
(3) pure level manganese sulfate will be analyzed to be dissolved in deionized water, in being sufficiently stirred under room temperature on magnetic stirring apparatus To being completely dissolved, solution C is obtained；
(4) solution B is added drop-wise in solution C dropwise under the conditions of magnetic agitation and obtains mixing turbid solution D；
(5) without ageing, directly mixing turbid solution D is filtered by circulating water type vacuum pump；Gained filter cake is transferred to In beaker, deionized water is added, is fully dissolved in magnetic stirring apparatus；
(6) repeat the above steps (5) 3-4 times, is finally washed 1-2 times with absolute ethyl alcohol；
(7) filter cake is transferred in pallet, puts and microwave treatment is carried out in micro-wave oven；The process of microwave treatment is：Micro- Microwave treatment 55s, the program of pause 5s reprocess 10 times under wave power 600-800W, and the microwave time amounts to 600s；
(8) sample after microwave treatment is transferred to 100 DEG C of dry 8-12h in air blast drying baker, ground afterwards up to institute State rod-like nano α-MnO2。
Wherein, the concentration of potassium permanganate and manganese sulfate is 0.1~0.5mol/L in the step (1) and (3).
The volume ratio of solution B and solution C is 1 in the step (4):4-5:1.
Rod-like nano α-the MnO2For hollow structure, a length of 0.5-3 μm, aperture 40-100nm of its footpath, specific surface area For 400-600m2/g。
In addition, the rod-like nano α-MnO being prepared by the method are also claimed in the present invention2And described bar-shaped receive Rice α-MnO2NO is reduced in low temperature selective catalysisXIn application.
Relative to the SCR catalyst of the prior art, beneficial effects of the present invention are：
(1) present invention utilize potassium permanganate Strong oxdiative reproducibility, be initially formed nanometer α existing for Thermodynamically stable- MnO2Crystal, then by being coordinated protective effect between the salpeter solution and manganese ion after dilution, improves nanometer α-MnO2Crystal Stability, finally using microwave rapid thermal treatment, under the microwave energy field action of high frequency conversion, the movement of molecule in order into OK, so as to quickly be assembled into rod-like nano α-MnO2；
(2) this hair prepares synthesis nanometer α-MnO2The cycle is short used in crystal, without being handled by hydro-thermal method long-time heat preservation, Without the cumbersome procedure by collosol and gel；Prepare synthesis nanometer α-MnO2Crystal yield is high, without high-temperature roasting, technique letter It is single, it is adapted to nanometer α-MnO2A large amount of preparations of crystal；That obtained by the present invention is a nanometer α-MnO2Crystal, purity is higher, has good Good low temperature selective catalysis processing NOXEffect.
Brief description of the drawings
Fig. 1 is 1 nanometer of α-MnO of embodiment2XRD diagram；
Fig. 2 is 1 nanometer of α-MnO of embodiment2SEM figure.
Fig. 3 is the embodiment of the present invention 1 and comparative example 1-2 catalyst activity evaluation result figures.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention is not It is limited only to the following examples.
Following embodiments unless specific instructions, the commercially available chemical reagent of reagent or industrial products of use.
Embodiment 1：
A kind of rod-like nano α-MnO2Preparation method, comprise the following steps：
(1) a certain amount of analytically pure potassium permanganate is dissolved in deionized water, it is complete in being stirred well under room temperature Dissolving, the liquor potassic permanganate A that configuration 80ml concentration is 0.1mol/L；
(2) 0.1mol/L dilute nitric acid solutions are added dropwise into solution A, adjusts PH to 6 or so, continues to stir evenly, obtain solution B；
(3) pure level manganese sulfate will be analyzed to be dissolved in deionized water, in being sufficiently stirred under room temperature on magnetic stirring apparatus To being completely dissolved, the manganese sulfate solution C that 80ml concentration is 0.2mol/L is configured；
(4) solution B is added drop-wise in solution C dropwise under the conditions of magnetic agitation and obtains mixing turbid solution D；
(5) without ageing, directly mixing turbid solution D is filtered by circulating water type vacuum pump；Gained filter cake is transferred to In beaker, 100mL deionized waters are added, are fully dissolved in magnetic stirring apparatus；
(6) repeat the above steps (5) 4 times, finally washed 2 times with absolute ethyl alcohol；
(7) filter cake is transferred in pallet, puts and microwave treatment is carried out in micro-wave oven；The process of microwave treatment is：Micro- Microwave treatment 55s, the program of pause 5s reprocess 10 times under wave power 700W, and the microwave time amounts to 600s；
(8) sample after microwave treatment is transferred to 100 DEG C of dry 10h in air blast drying baker, ground afterwards up to described Rod-like nano α-MnO2。
Rod-like nano α-the MnO2XRD diagram and SEM figures see Fig. 1, Fig. 2.
Embodiment 2：
A kind of rod-like nano α-MnO2Preparation method, comprise the following steps：
(1) a certain amount of analytically pure potassium permanganate is dissolved in deionized water, it is complete in being stirred well under room temperature Dissolving, the liquor potassic permanganate A that configuration 80ml concentration is 0.2mol/L；
(2) 0.1mol/L dilute nitric acid solutions are added dropwise into solution A, adjusts PH to 6 or so, continues to stir evenly, obtain solution B；
(3) pure level manganese sulfate will be analyzed to be dissolved in deionized water, in being sufficiently stirred under room temperature on magnetic stirring apparatus To being completely dissolved, the manganese sulfate solution C that 80ml concentration is 0.2mol/L is configured；
(4) solution B is added drop-wise in solution C dropwise under the conditions of magnetic agitation and obtains mixing turbid solution D；
(5) without ageing, directly mixing turbid solution D is filtered by circulating water type vacuum pump；Gained filter cake is transferred to In beaker, 100mL deionized waters are added, are fully dissolved in magnetic stirring apparatus；
(6) repeat the above steps (5) 3 times, finally washed 1-2 times with absolute ethyl alcohol；
(7) filter cake is transferred in pallet, puts and microwave treatment is carried out in micro-wave oven；The process of microwave treatment is：Micro- Microwave treatment 55s, the program of pause 5s reprocess 10 times under wave power 800W, and the microwave time amounts to 600s；
(8) sample after microwave treatment is transferred to 100 DEG C of dry 12h in air blast drying baker, ground afterwards up to described Rod-like nano α-MnO2。
Embodiment 3：
A kind of rod-like nano α-MnO2Preparation method, comprise the following steps：
(1) a certain amount of analytically pure potassium permanganate is dissolved in deionized water, it is complete in being stirred well under room temperature Dissolving, the liquor potassic permanganate A that configuration 80ml concentration is 0.2mol/L；
(2) 0.1mol/L dilute nitric acid solutions are added dropwise into solution A, adjusts PH to 6 or so, continues to stir evenly, obtain solution B；
(3) pure level manganese sulfate will be analyzed to be dissolved in deionized water, in being sufficiently stirred under room temperature on magnetic stirring apparatus To being completely dissolved, the manganese sulfate solution C that 80ml concentration is 0.3mol/L is configured；
(4) solution B is added drop-wise in solution C dropwise under the conditions of magnetic agitation and obtains mixing turbid solution D；
(5) without ageing, directly mixing turbid solution D is filtered by circulating water type vacuum pump；Gained filter cake is transferred to In beaker, 100mL deionized waters are added, are fully dissolved in magnetic stirring apparatus；
(6) repeat the above steps (5) 3 times, finally washed 2 times with absolute ethyl alcohol；
(7) filter cake is transferred in pallet, puts and microwave treatment is carried out in micro-wave oven；The process of microwave treatment is：Micro- Microwave treatment 55s, the program of pause 5s reprocess 10 times under wave power 600W, and the microwave time amounts to 600s；
(8) sample after microwave treatment is transferred to 100 DEG C of dry 8h in air blast drying baker, ground afterwards up to the rod Shape nanometer α-MnO2。
Embodiment 4：
A kind of rod-like nano α-MnO2Preparation method, comprise the following steps：
(1) a certain amount of analytically pure potassium permanganate is dissolved in deionized water, it is complete in being stirred well under room temperature Dissolving, the liquor potassic permanganate A that configuration 80ml concentration is 0.25mol/L；
(2) 0.1mol/L dilute nitric acid solutions are added dropwise into solution A, adjusts PH to 6 or so, continues to stir evenly, obtain solution B；
(3) pure level manganese sulfate will be analyzed to be dissolved in deionized water, in being sufficiently stirred under room temperature on magnetic stirring apparatus To being completely dissolved, the manganese sulfate solution C that 80ml concentration is 0.25mol/L is configured；
(4) solution B is added drop-wise in solution C dropwise under the conditions of magnetic agitation and obtains mixing turbid solution D；
(5) without ageing, directly mixing turbid solution D is filtered by circulating water type vacuum pump；Gained filter cake is transferred to In beaker, 100mL deionized waters are added, are fully dissolved in magnetic stirring apparatus；
(6) repeat the above steps (5) 4 times, finally washed 2 times with absolute ethyl alcohol；
(7) filter cake is transferred in pallet, puts and microwave treatment is carried out in micro-wave oven；The process of microwave treatment is：Micro- Microwave treatment 55s, the program of pause 5s reprocess 10 times under wave power 750W, and the microwave time amounts to 600s；
(8) sample after microwave treatment is transferred to 100 DEG C of dry 10h in air blast drying baker, ground afterwards up to described Rod-like nano α-MnO2。
Comparative example 1
A kind of nanometer MnO2Preparation method, comprise the following steps：
(1) a certain amount of analytically pure potassium permanganate is dissolved in deionized water, it is complete in being stirred well under room temperature Dissolving, the liquor potassic permanganate A that configuration 80ml concentration is 0.1mol/L；
(2) 0.1mol/L dilute nitric acid solutions are added dropwise into solution A, adjusts PH to 6 or so, continues to stir evenly, obtain solution B；
(3) pure level manganese sulfate will be analyzed to be dissolved in deionized water, in being sufficiently stirred under room temperature on magnetic stirring apparatus To being completely dissolved, the manganese sulfate solution C that 80ml concentration is 0.2mol/L is configured；
(4) solution B is added drop-wise in solution C dropwise under the conditions of magnetic agitation and obtains mixing turbid solution D；
(5) the turbid D of step (4) is transferred in hydrothermal reaction kettle, is taken out at 160 DEG C after hydro-thermal reaction 12h, from The heart, be washed with deionized to neutrality；
(6) sample after washing is transferred to 100 DEG C of dry 10h in air blast drying baker, ground afterwards up to the nanometer MnO2。
Comparative example 2
A kind of nanometer MnO2Preparation method, comprise the following steps：
(1) a certain amount of analytically pure potassium permanganate is dissolved in deionized water, it is complete in being stirred well under room temperature Dissolving, the liquor potassic permanganate A that configuration 80ml concentration is 0.1mol/L；
(2) 0.1mol/L dilute nitric acid solutions are added dropwise into solution A, adjusts PH to 6 or so, continues to stir evenly, obtain solution B；
(3) by the dissolving of 2g fumaric acid again 50mL distilled water, electric jacket dissolves by heating, and is protected in 50 DEG C of waters bath with thermostatic control Temperature, it is stand-by；
(4) fumaric acid solution is added drop-wise in solution B dropwise under the conditions of magnetic agitation, stirring reaction 30min, obtains MnO2 Colloidal sol；
(5) under magnetic stirring, as step (4) MnO210mL gelling agent triethylamines are added in colloidal sol, through magnetic agitation 1h Washed 4 times with water and ethanol respectively afterwards, 12h is then dried in 50 DEG C of vacuum drying chambers up to rice MnO2。
Activity rating is carried out to the performance of the embodiment of the present invention 1 and comparative example 1-2 catalyst
The technical process of experiment：
Denitration activity test is carried out to catalyst obtained by embodiment 1 and comparative example 1-2 respectively, SCR denitration experiment is being made by oneself Carried out in tubular fixed-bed SCR reactors, internal diameter 10mm.Catalytic reactor is external electric, with insertion catalyst layer Thermocouple measuring temperature, uses temperature controller controlling reaction temperature.
Experiment uses standard steel cylinder gas simulative power plant flue gas.Since NO accounts for more than 95%, NO in typical flue gas NOx2Shadow Very little is rung, can be ignored, so the NOx in experiment is replaced using NO.The composition of gaseous mixture is NO-0.0865%, O2- 0.83%, NH3- 0.0865%, N2For carrier gas, total flow maintains 800mL/min, and corresponding gaseous state air speed is 5000h-1, it is Avoid NH3Influence to NOx tests, flue gas wash NH before flue gas analyzer is entered with phosphoric acid solution3.Before and after reaction NO and O2Content 2000 flue gas analysis measuring instruments of Rosemount NGA, the denitration activity of catalyst represents with the conversion ratio X of NO：
Test result is as shown in figure 3, rod-like nano α-MnO prepared by embodiment 12Catalytic performance be substantially better than contrast Example 1 and comparative example 2.
It is above-mentioned to be illustrated for exemplary embodiment, it should not be construed as limiting the invention.For fields Those of ordinary skill for, other different forms of changes or modifications may be made based on the above description.Here There is no need to be enumerated to all embodiments.And the obvious changes or variations thus extended out still in Among the protection domain of the invention.

Claims (5)

  1. A kind of 1. rod-like nano α-MnO2Preparation method, it is characterised in that comprise the following steps：
    (1) a certain amount of analytically pure potassium permanganate is dissolved in deionized water, is completely dissolved in being stirred well under room temperature, Obtain solution A；
    (2) 0.1mol/L dilute nitric acid solutions are added dropwise into solution A, adjusts PH to 6 or so, continues to stir evenly, obtain solution B；
    (3) pure level manganese sulfate will be analyzed to be dissolved in deionized water, in being stirred well under room temperature on magnetic stirring apparatus Fully dissolved, obtains solution C；
    (4) solution B is added drop-wise in solution C dropwise under the conditions of magnetic agitation and obtains mixing turbid solution D；
    (5) without ageing, directly mixing turbid solution D is filtered by circulating water type vacuum pump；Gained filter cake is transferred to beaker In, deionized water is added, is fully dissolved in magnetic stirring apparatus；
    (6) repeat the above steps (5) 3-4 times, is finally washed 1-2 times with absolute ethyl alcohol；
    (7) filter cake is transferred in pallet, puts and microwave treatment is carried out in micro-wave oven；The process of microwave treatment is：In microwave work( Microwave treatment 55s, the program of pause 5s reprocess 10 times under rate 600-800W, and the microwave time amounts to 600s；
    (8) sample after microwave treatment is transferred to 100 DEG C of dry 8-12h in air blast drying baker, ground afterwards up to the rod Shape nanometer α-MnO2；
    Rod-like nano α-the MnO2For hollow structure, a length of 0.5-3 μm, aperture 40-100nm, specific surface area 400- of its footpath 600m2/g。
  2. 2. rod-like nano α-MnO according to claim 12Preparation method, it is characterised in that in the step (1) and (3) The concentration of potassium permanganate and manganese sulfate is 0.1~0.5mol/L.
  3. 3. according to any one of the claim 1-2 rod-like nano α-MnO2Preparation method, it is characterised in that the step (4) The volume ratio of middle solution B and solution C is 1:4-5:1.
  4. 4. the rod-like nano α-MnO2 being prepared according to any one of claim 1-3 the method.
  5. 5. the application of rod-like nano α-MnO2 described in a kind of claim 4, it is characterised in that the rod-like nano α-MnO2 are low Application in warm selective catalysis reduction NOX.
CN201711083081.6A 2017-11-07 2017-11-07 A kind of rod-like nano α-MnO2And its preparation method and application Withdrawn CN108017091A (en)

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CN111384366A (en) * 2018-12-27 2020-07-07 浙江浙能中科储能科技有限公司 alpha-MnO 2 Carbon/carbon composite electrode material and preparation method and application thereof
CN114105204A (en) * 2021-11-12 2022-03-01 中博龙辉装备集团股份有限公司 Rod-shaped manganese oxide and preparation method and application thereof
CN114377686A (en) * 2022-01-26 2022-04-22 华中师范大学 Microwave positioning assembly-based electric joule heating catalytic material and preparation method thereof
CN115025771A (en) * 2022-05-25 2022-09-09 广东工业大学 Rod-shaped beta-MnO 2 Catalyst, preparation method and application thereof

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111384366A (en) * 2018-12-27 2020-07-07 浙江浙能中科储能科技有限公司 alpha-MnO 2 Carbon/carbon composite electrode material and preparation method and application thereof
CN111384366B (en) * 2018-12-27 2021-05-07 浙江浙能中科储能科技有限公司 alpha-MnO 2 Carbon/carbon composite electrode material and preparation method and application thereof
CN114105204A (en) * 2021-11-12 2022-03-01 中博龙辉装备集团股份有限公司 Rod-shaped manganese oxide and preparation method and application thereof
CN114377686A (en) * 2022-01-26 2022-04-22 华中师范大学 Microwave positioning assembly-based electric joule heating catalytic material and preparation method thereof
CN114377686B (en) * 2022-01-26 2024-04-02 华中师范大学 Electric joule heating catalytic material based on microwave positioning assembly and preparation method thereof
CN115025771A (en) * 2022-05-25 2022-09-09 广东工业大学 Rod-shaped beta-MnO 2 Catalyst, preparation method and application thereof

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